Resin drying catalysis



United States Patent RESIN DRYING CATALYSIS Rene Leclercq,Woluwe-Saint-Pierre, and Ren Paquet, Braine-le-Comte, Belgium, assignorsto Union Chimique Belge S.A., Brussels, Belgium, a corporation ofBelgium No Drawing. Application June 4, 1957 Serial No. 663,334

Claims priority, application Belgium June 22, 1956 1 Claim. (Cl. 260-18)The resins obtained according to our copending patent applicationsSerial No. 628,000, filed December 13, 1956; Serial No. 663,363,'filedJune 4, 1957, and entitled Preparation of Resins From Diisocyanates; andSerial No. 663,364, filed June 4, 1957, and entitled Process forthePreparation of Resins From Abietyl Alcohols, now US. Patent No.2,867,644; are starting materials for the manufacture of varnishes whichresist chemical agents. Experience has shown that these varnishes mustbe dried inan oven at a temperature of at least 100 C.

The resins of application Ser. No. 663,363 are prepared by heating atleast one diisocyanate of the general formula OCN-R--NCO, wherein R is amember selected from the group consisting of aliphatic and aromaticbivalent radicals, with a mixture of at least two monohydroxylatedcompounds selected from the group consisting of allyl, benzyl, furfuryland abietyl alcohols, phenol and nonylphenol.

It has now been found that the aforementioned heating necessary to dryvarnishes prepared from such resins can be avoided by the use of asuitable catalyst. In this way, resins are obtained which dry in air butwhich have not always exactly the properties of the resins dried in anoven, that is to say,'the resistance thereof, while remainingconsiderable, may be different. The catalyst is formed by anorganometallic compound selected from the group consisting of lead,cobalt, tin and alkyl-tin salts of organic acids and organic esters oftitanic, stannic and zirconic acids, or even by a mixture of theaforementioned organometallic compounds.

The quantity of catalyst to be employed is about 3% by weight of theresin, the extreme quantities of the catalyst being 0.5% and 20%.

The organometallic compounds which can be used in the present inventionare very numerous. There are more especially to be mentioned:

Lead or cobalt octanoate and 2-ethyl-hexanoate,

Dibutyl-tin dilaurate,

Di-n-octyl-tin monobutyl maleate,

Di-n-octyl-tin bis-(Z-ethyl hexanoate),

Di-n-octyl-tin dibutyl thioacetate,

Tetralkyl stannates (alkyl containing from 2 to 8 carbon atoms and moreespecially tetrabutyl stannate),

Tetralkyl zirconates (alkyl containing from 2 to 8 carbon atoms),

Tetralkyl titanates (alkyl containing from 2 to 8 carbon atoms and moreespecially tetrabutyl titanate),

A series of titanium esters sold by E. I. du Pont de Nemours & Co., suchas:

TAT6-211 (=triethanolamine titanate-N-stearate), TAT-O-21l(=triethanolamine' titanate-N-oleate), OGT-31 (=octylene glycoltitanate),

TAT-21 (=triethanolamine titanate),

which are compounds of titanium with triethanolamine or octylene glycolor fatty esters of these compounds.

This list is not limitative. It is necessary to add an ethylenic,acetylenic or abietyl monoalcohol or an alkylated phenol when themonoalcohols or monophenols used for the preparation of the resins donot contain at least one double bond or an alkylated phenyl radical. Thequantity of these alcohols which is necessary varies within very widelimits: depending on the resins and the nature of the monoalcohol, 1-40%of the weight of the resin are added.

Example 1 A resin is prepared by heating 168 g. of hexamethylenediisocyanate (commercial product Desmodur H of Farbenfabriken BayerA.G.), 75.2 g. of phenol and 53.2 g. of abietyl alcohols in the form ofAbitol to 170 C.

50 g. of this resin are dissolved in 50 g. of toluene/ 3 cc. oftetrabutyl titanate are added to this solution. A

varnish is obtained which is dust-free in 1 to 2 hours and alcohols inthe form of Abitol at 170 C.

50 g. of this resin are dissolved in 50 g. of toluene.

2 cc. of lead-octanoate containing 24% of Pb are added to this solution.A varnish is obtained which is dustfree in 1 to 2 hours and which isresistant even to strong acids I Example 3 y A resin is prepared byheating 168 g. of hexamethylene diisocyanate (Desmodur H), 30 g. ofallyl alcohol and 133g. of abietyl alcohols in the form of Abitol to170C.

50 g. of this resin are dissolved in 50 g. of toluene. 2

cc. of lead octanoate containing 24% of- Pb are added to this solution.A varnish is obtained which is dustfree in about 2 hours and whichresists to even strong concentrated bases, even concentrated sulphuricacid and dilute hydrochloric and nitric acids.

Example 4 A resin is prepared by heating 168 g. of hexamethylenediisocyanate (Desmodur H) and 205 g. of octyl phenol to 170 C. 50 g. ofthis resin are dissolved in 50 g. of toluene and 3 cc. oftriethanolamine titanate-N-stearate (TATS211 of E. I. du Pont de Nemours& Co.) are added to this solution. A varnish is obtained which isdust-free after 3 to 4 hours.

Example 5 Example 6 The toluenic solution of the resin obtained inExample 2 is treated with 12 cc. of a 33% solution in toluene ofdin-octyl-tin bis-(2-ethyl hexanoate). A varnish is obtained which isdust-free in 1 to 2 hours when spread on a plate.

Example 7 The resin solution obtained in Example 3 is treated with 6 cc.of a 33% solution in toluene of di-n-octyltin dibutyl thioacetate. Avarnish, spread on a plate, is dust-free after 1 to 2 hours.

3 Example 8 The toluenic solution of the resin obtained in Example 3 istreated with 12 cc. of a 33% solution in toluene of tin-dibutyldilaurate.. A varnish is' obtained which; whenspread on a plate, isdust-free in two hours.

Example 9 A resin is prepared by heating 168 g. of hexamethylenediisocyanate and 219' g.- of nonylphenol to 170 C. 50 g. ofthis resinare dissolved in.50 g. of toluene and 4 cc. of lead octanoate containing24% of Pb are added. A varnish is obtained which is dust-free in 1 to 2hours when spread on a plate.

Example 10 A resin is prepared by heating 168 g."of 'hexamethylenediisocyanate and.124 g. of l-ethynyl cyclohexanol to 170 C;

50g. of this resin are dissolved in 50g. of toluene and '3 cc. oftetrabutyl titanate are added. A varnish is obtained which is dust-freein l to 2 hours.

Example, 11

The toluenic solution of the resin obtained in Example 4 is treated with2 cc. of cobalt octanoate containing 6% of Co and 2 cc. of OGT-31(octylene glycol titanate).

A varnish is obtained which is dust-free in 2 hours.

Example 12 A resin is prepared by heating 168. g. of hexamethylenediisocyanate, 20 g. of allyl alcohol, 88.6 g. of abietyl alcohols in theform of Abitol and 31.3 g. of phenol at Example 13 Toluenic solution ofthe resin obtained in Example 4 is. treated with 3 cc. of tetrabutylstannate. Avarnish is obtained which is dust-free in 3 to 4 hours.

Example 14 The toluenic solution of the resins obtained in Examples 1and 4 are treated with 3 cc.'of OGT-31 (octylene glycol titanate).varnishes are obtained which are dust-free in 3 to 4 hours.

4 Example 15 The toluenic solution of the resin obtained in Example 12is treated with 3 cc. of 6% Zirco Drier Catalyst" of Advance Solventsand Chemical Corporation. A varnish is obtained which .is dust-.free in1 to 2 hours.

Example 16 The toluenic solution of the resin obtained in Example 4 istreated with 2 cc. of lead octanoate' containing 24% of Pb. vA varnishis obtained which is dust-free in 1 to 2 hours and which has a goodresistance to even concentrated sulphuric acid and to dilute nitricacid.-

Ex'ample 17 A resin is prepared by heating 134.4 g. of hexamethylenediisocyanate, 59.2 g; of 3,3'-dimethoxy-4,4'-dipheny1- ene diisocyanate(commercial product Dadi of The Carwin Co.), and 266 g. ofabietylalcohols in:the form of. Abitol at 170 C."

g. oftheresin'obtained are dissolved in 50 got tolueneandi2 cc. oftetrabutyl titanate are added. A varnish 'is obtained WhiChiS dust-freein A to 1 hour.

We claim:

An air-drying varnish composition consisting essentially of (1) anorganic solution of a resin,,said resin being obtained by heating (a) atleast one diisocyanate of the general formula OCN-R-NCO wherein R is amember selected fromthegroupconsisting of aliphatic and aromaticbivalent radicals with .(b) a mixture of at least two monohydroxylatedcompounds selected. from the group consisting of allyl, benzyl,furfuryl, and abietyl alcohols, phenol and nonylphenol and"(2) from 0.5to 20% by Weightof a catalytic drier containing tinand selected from thegroup consisting of tetrabutyl stannate, dibutyl tin dilaurate anddFn-octyl-tin bis-(Z-ethyl hexanoate).

References Cited in the fileiof this patent UNITED STATES PATENTS2,374,136 Rothrock Apr. 17, 1945 2,720,468 Shacklett Oct. 11, 19552,801,990 Seeger et a1 Aug. 6, 1957 OTHER REFERENCES Titanium OrganicsShow Promise, Chem. & Eng. News, pages 4226-8, Oct. 3,1955.

